Quench Al.qxp 4/27/2009 2:26 PM Page 1 QUENCHING FUNDAMENTALS QUENCHING OF : ALUMINUM ALLOYS PROPERTY PREDICTION BY QUENCH FACTOR ANALYSIS Quench factor analysis During solutionizing of alu- quenching process. The objective is to minum alloys, the alloying el- quench sufficiently fast to avoid the (QFA) is a method used to ements are dissolved in the undesirable concentration of alloying predict the properties of aluminum lattice structure of elements in the defect and grain the solid solution, and the ob- boundary structure while at the same heat treatable aluminum jective is to maximize the concentra- time, not quenching faster than neces- alloys from cooling tion of these elements, which include sary to minimize residual stresses, copper, zinc, magnesium, and silicon which may lead to excessive distortion (time-temperature) curves. in the solid solution[1]. The concentra- or cracking[2, 3]. After quenching, the tion and rate of dissolution of these el- aluminum alloy is aged. During the Although the QFA ements in the solid solution increase aging process, hardening elements pre- procedure has evolved since with increasing temperature. cipitate in localized areas, which sig- The aluminum alloy is cooled after nificantly increases the strength of the its original introduction, the solutionizing. If cooling is too slow, the part. original procedure alloying elements diffuse through the Fink and Willey performed an ex- solid solution and concentrate at grain tensive study on the effects of quench- continues to be successfully boundaries, large voids, undissolved ing on the strength of 7075-T6[4]using used for prediction of yield particles, and other “defect” locations. isothermal quenching techniques. This The diffusion process is slower for was done by constructing C-curves and tensile strength, some alloys than others, thus permit- (Fig. 1), which are plots of times re- corrosion and other ting slower cooling rates during quired to precipitate sufficient alloy quenching. For optimal properties, it content to change the strength by a properties. is desirable to retard this diffusion certain amount. They identified the process and maintain the alloying el- critical temperature range; the range ements in solid solution. For quench- that provided the highest precipitation Patricia Mariane Kavalco hardenable wrought alloys (2xxx, 6xxx, rates[5]. It is important to note that al- and Lauralice C. F. Canale* and 7xxx, and casting alloys such as though critical solute temperature may 356), this is accomplished by the be identified from a C-curve for an University of São Paulo São Carlos, SP, Brazil George E. Totten, FASM** Portland State University Portland, OR *Member of ASM International **Member of ASM International and member, Representative drop bottom furnace for heat treating and quenching aluminum alloys. Courtesy of ASM Heat Treating Society D. Scott MacKenzie, Houghton International Inc. HEAT TREATING PROGRESS • MAY/JUNE 2009 23 Quench Al.qxp 4/27/2009 2:26 PM Page 2 alloy (for example, 340°C for 7075-T73), (seconds) to cool from 400 to 290°C, the specific C-curve obtained varies which will yield an average cooling depending on the property being rate in °C/s. This is the classical ap- measured[6]. proach upon which most standards for Various studies were conducted the heat treatment of aluminum alloys after Fink and Willey’s work to deter- are written. The maximum attainable mine the relative quench rate sensi- strength properties are dependent on tivity to yield different properties for the average cooling rate. Generally, various alloys. Figure 2 illustrates the faster cooling rates provide greater effect of cooling rate on tensile strength strengths up to a limit. for different aluminum alloys and tem- The traditional approach for mod- pers[5]. The average cooling rate tradi- eling quench sensitivity (which refers tionally has been defined to be the time to the amount age hardening response is reduced by slow quench cooling) to quantitatively correlate quenching 448800 cooling rate with mechanical proper- ties of aluminum alloys presumes a 110000 linear, well-behaved cooling process 442255 9988 9900 between 400 and 290°C. However, this is seldom the case, and, therefore, the 8800 classical method of determining the 337700 average cooling rate of aluminum al- hh ggtt loys may fail when the quenching nn ee,, °°CC 331155 mm ssttrree prurpocteedss o irs dneolnayliende aqru, seuncchh iansg a pnr oincetesrs-. uurr mmuu Therefore, it is desirable to use an al- eerraatt aaxxii ternative process, quench factor pp mm eemm 226600 ooff analysis (QFA), that correlates actual TT %% cooling pathway by using a cooling 8800 curve (time-temperature curve) of the 220055 9900 actual cooling process throughout the quenching cycle for the quenching 9988 process and cross section size being 115500 TTeennssiillee ssttrreennggtthh 110000 used with a C-curve (time-tempera- YYiieelldd ssttrreennggtthh ture-property curve) for the specific alloy of interest[7,8]. QFAis now used 9933 routinely by many researchers in 00..11 11 1100 110000 11,,000000 the aluminum thermal processing TTiimmee,, ss industry. Over the approximately 25 years Fig. 1 —C-Curves illustrating the effect of alloy precipitation on tensile strength for 7075-T6 generated by Fink and Willey. since QFAwas introduced, the original model has undergone considerable AAvveerraaggee ccoooolliinngg rraattee ((440000 ttoo 229900°°CC)),, °°CC//ss evolution and improvement. The ob- 110000 11 1100 110022 110033 110044 jective here is review the classical model, which still has a great deal of 77117788-TT66 utility as it exists, and to highlight 9900 660000 some potential limitations. 77007755-TT66 Discussion 8800 77005500-TT7733 77005500-TT7733 Avrami used isothermal kinetics to eennggtthh,, kkssii 7700 2222000022114444--TTTT4466 550000 nnggtthh,, MMPPaa suetroutuidesys c tooroaf lnianslgfuo pmrmrionacuetismosne s ad[9lu,l1o0r]yi.n Tsg h acero epn rtodipne--- nnssiillee ssttrr 6600 66007700-TT66 440000 ssiillee ssttrree pperencdipenitta tioonn ththea ta moocucunrts ofd uarlilnoyg TTee eenn cooling, regardless of the cooling TT 5500 pathway. The Avrami Equation for 66006611-TT66 330000 isothermal precipitation kinetics is[5]: 4400 (1) 3300 220000 where ζ = fraction of precipitation 11 1100 110022 110033 110044 110055 which has occurred in time tduring AAvveerraaggee ccoooolliinngg rraattee ((775500 ttoo 555500°°FF)),, °°FF//ss the quench, and k = temperature-in- Fig. 2 —Tensile strength as a function average cooling rate for different aluminum alloys and tempers. dependent constant (s). The value of k 24 HEAT TREATING PROGRESS (cid:127) MAY/JUNE 2009 Quench Al.qxp 4/28/2009 1:16 PM Page 3 depends on the degree of supersatu- 555500 ration and the rate of diffusion, and is determined from the following 550000 equation developed by Evancho and 445500 ∆ttii CC TTii Staley[5]: 440000 CC 335500 ee,, °° uurr 330000 aatt (2) eerr 225500 pp where C = critical time (s) required to mm T ee 220000 precipitate a constant fraction (the equa- TT 115500 tion of the C-curve), k = a constant that 1 QQ == ∑∆ttii // CC equals the natural logarithm of the 110000 TTii fraction untransformed (1 - fraction 5500 defined by the C-curve); if 0.5% is un- 00 transformed, then k = -ln(σ/σmax) = 1100-22 1100-11 110000 110011 110022 110033 1 CCrriittiiccaall ttiimmee,, ss -0.005013, R= ideal gas constant = 8.3143 J.K-1.mol-1, and T = temperature (K). Fig. 3 —Schematic illustration of the experimental method used for calculating a quench factor. The values of k – k are determined 2 5 by multiple linear regression analysis ical time (s) from the C-curve and is quench factor by[5,14]: to obtain the best fit to the CT equation calculated from Eq 5, t = time from the by repeated iterations until minimum cooling curve (s), t0= time at the start (5) computational error is obtained[5]. A of the quench (s), and tf = time at the summary of reported k-values for finish of the quench (s). When Q= 1, where σy= predicted yield strength yield strength that have reported to the fraction transformed equals the (MPa), σmax = yield strength (MPa) date are provided in Table 1[11]. fraction represented by the C-curve. after an infinite quench (and aging From these relationships, it is pos- By the Rule of Additivity, the temper- cycle), e = base of the natural loga- sible to redefine the equation for the ature-time curve is divided into a se- rithm, K1= -ln(0.995) = -0.00501, and amount of solute precipitated during ries of isothermal time steps as de- Q = quench factor. This relationship is the quench which is called the quench scribed by Evancho and Staley[5]. For shown graphically in Fig. 4 for the factor, traditionally designated as “Q”. each time step, the volume fraction of yield strength of 7075-T73. Cahn showed that transformations the new phase that is formed during In their 1974 paper, Evanco and that nucleate heterogeneously, such as this time step is calculated by isothermal Staley showed that from the Avrami aluminum alloys, obey the Rule of Ad- kinetics using the Avrami Equation. This Equation, the attainable strength ditivity, which states that reactions are is shown in Fig. 3, where the quench is a function of the amount of additive and therefore transformation factor Qis obtained by combining the solute remaining in solution after kinetics for nonisothermal conditions, cooling curve for the quenching process the quench and is related to k as 1 such as those that would be present with the C-curve and the value for Qis follows[5]: during a typical quenching process obtained by[5,13]: may be described by[12]: (6) (3) (4) where σ = 0.995 × σ . x max The maximum and minimum al- where: Q= measure of the amount In the original classical approach, lowable values may be determined ex- transformed (quench factor), C = crit- properties were predicted from the perimentally, or values obtained from T Table 1 —Coefficients for Calculating Quench Factors at 99.5% of Attainable Yield Strength Alloy k(a) k, s k, J/mol k, K k, J/mol Calculated range, °C Ref. 1 2 3 4 5 7010-T76 -0.00501 5.6 ×10-20 5780 897 1.90 ×105 425-150 20 7050-T76 -0.00501 2.2 ×10-19 5190 850 1.8 ×105 425-150 5 7075-T6 -0.00501 4.1 ×10-13 1050 780 1.4 ×105 425-150 5 7075-T73 -0.00501 1.37 × 10-13 1069 737 1.37 ×105 425-150 21 7175-T73 -0.00501 1.8 × 10-9 526 750 1.017×105 425-150 12 2017-T4 -0.00501 6.8 × 10-21 978 822 2.068×105 425-150 21 2024-T6 -0.00501 2.38 × 10-12 1310 840 1.47 ×105 425-150 22 2024-T851 -0.00501 1.72 ×10-11 45 750 3.2×104 425-150 23 2219-T87 -0.00501 0.28 × 10-7 200 900 2.5 ×104 425-150 24 6061-T6 -0.00501 5.1 × 10-8 412 750 9.418×104 425-150 21 356-T6 -0.0066 3.0 × 10-4 61 764 1.3 ×105 425-150 25 357-T6 -0.0062 1.1 × 10-10 154 750 1.31 ×105 425-150 25 Al-2.7Cu-1.6Li-T8 -0.0050 1.8 × 10-8 1520 870 1.02 ×105 425-150 25 (a) k1is a unitless value that corresponds to the unprecipitated fraction. For this analysis, it is usually 0.995 and ln 0.995 = -0.00501. HEAT TREATING PROGRESS • MAY/JUNE 2009 25 Quench Al.qxp 4/27/2009 2:26 PM Page 4 Table 2 —Relationship between quench factor and yield strength in 7075-T73(a) Quench Attainable Predicted Quench Attainable Predicted factor (Q) yield strength, % yield strength, MPa Factor (Q) yield strength, % yield strength, MPa 0.0 100.0 475.1 26.0 87.8 417.2 2.0 99.0 470.2 28.0 86.9 413.0 4.0 98.0 465.4 30.0 86.0 408.9 6.0 97.0 461.3 32.0 85.2 404.7 8.0 96.1 456.5 34.0 84.3 400.8 10.0 95.1 451.6 36.0 83.5 396.5 12.0 94.2 447.5 38.0 82.7 393.0 14.0 93.2 442.7 40.0 81.8 388.9 16.0 92.3 438.5 42.0 81.0 384.7 18.0 91.4 434.4 44.0 80.2 381.3 20.0 90.5 429.6 46.0 79.4 377.2 22.0 89.6 425.4 48.0 78.6 373.7 24.0 88.7 421.3 50.0 77.8 369.6 (a) σmax= 475.1 MPa used for high-strength alloys because 660000 σ << σ [4]. Staley, et.al., also sub- min max sequently stated that this assumption for σ was made because the strength min 550000 of aluminum alloys held for infinitely 66 44445544 443333443311335544332222339988223388221111224422113344990011661111113333883355 ltounreg wtimouelsd b beleo zwe rtoh[e16 s].o lFvuurst hteemrmpeorrae-, this simplification was validated by 440000 2299 PPaa 3377 the excellent fit that the simplified MM hh,, value for k1provided for C-curve data ggtt 2244 developed for 7075-T6 and 2024-T4[5]. nn 330000 1111 dd SSttrree 3344 Fporor vmidanesy ainddeuqustaritael raepspullitcsa wtiohnesn, tthhies YYiieell σyy == σmmaaxxeeKK11QQ loss in properties is less than 10%[15]. 220000 However, Swartzendruber, et.al., sub- sequently recommended that Eq 6 was necessary to minimize predictive errors[17]. 110000 From these equations, a number of observations are made regarding the quenching process showing the power 00 of QFAin quench process design and 11 1100 110022 110033 QQuueenncchh ffaaccttoorr ((QQ)) analysis: (cid:127) Low values of Qare associated Fig. 4 —Yield strength of aluminum 7075-T73 as Mil Handbook 5may be used to obtain with high quench rates, minimum pre- a function of quench factor of the material. an estimation of the property of in- cipitation during cooling and high terest under the experimental yield strengths. quenching conditions. Table 2 shows (cid:127) Conversely, higher Q-values are the relationship between quench factor obtained with slower quench rates and and yield strength for 7075-T73 re- are associated with lower strength ported previously[8]. values. When Evancho and Staley analyzed (cid:127) An alloy with a low rate of precip- 7075-T6 and 2024-T4 interrupted itation will produce a lower quench quenching data previously published factor Qthan an alloy with a high pre- by Fink and Willey, they obtained a cipitation rate at the same cooling rate. linear correlation for log (σ/σ ) (cid:127) Quench factors calculated for dif- min versus isothermal holding time, and ferent alloys might be different even if the slope was equal to 1.Therefore, similar section sizes are cooled in the they set σ = 0 in Eq 9 to predict the same quenchant, because quench fac- min extent of transformation in their early tors take into account individual alloy work[5,15]. In their 1974 paper, Staley precipitation kinetics by means of the and Evancho further noted that the equation describing the C-curve (C T simplified equation for k could be function) for each alloy. 1 26 HEAT TREATING PROGRESS (cid:127) MAY/JUNE 2009 Quench Al.qxp 4/27/2009 2:26 PM Page 5 (cid:127) Solute elements are precipitated IInnsseerrtt hhaannddllee ffuullll ddeepptthh during cooling from the solution WWeelldd wwaatteerr ttiigghhtt treating temperature at high Q-values. As a consequence, an improperly quenched alloy may not properly 2255..44 mmmm harden during aging, and it may be susceptible to intergranular corrosion, 5500 mmmm stress corrosion, or exfoliation. The quench factor provided by a 110000 mmmm particular quenchant or quenching process can be determined experimen- Fig. 5 —Aluminum bar probe (a) and aluminum tally by using parts, or sheet, bar, or sheet probe (b) plate probes instrumented with ther- culated data for some coefficients[19]. mocouples such as those illustrated in Fig. 5. The time-temperature data ob- Conclusions tained upon immersion of the solution- To achieve the ideal quench, low PPrroobbee hhaannddllee ized instrumented probe (or part) is values of Qare desirable because they collected using a data-acquisition are associated with high quench rates, system. The time step used in the minimum precipitation during cooling, TThheerrmmooccoouuppllee above calculation for Qis typically as- and high yield strengths. High values wwiirree wweellddeedd sumed to be the data collection fre- of Q can lead to an improperly WWaatteerr ttiigghhtt ttoo sshheeeett cceenntteerr quency. The effect of the time step on quenched alloy that may not properly the Q-value is shown in Table 3[8]. harden during aging and may be sus- Although QFAhas been, and con- ceptible to intergranular corrosion, tinues to be, used successfully for prop- stress corrosion, or exfoliation. erty prediction of heat treatable alu- Classical QFAhas been used suc- minum alloys, there are limitations to cessfully for property prediction of 22 iinn.. the predictive accuracy which include: heat treatable aluminum alloys. How- (cid:127) Classical QFAassumes that trans- ever, there are limitations to the pre- formational kinetics are described by dictive accuracy of the classical equa- a special case of the Avrami Equation tions, which are attributable to the where the Avrami coefficient is n= 1. assumptions made in the theoretical However, n= 1 is mostly related to for- development. Newer predictive 22 iinn.. mation of non-hardening precipitates methodologies that address these lim- within grains during quenching. itations and expand the potential (cid:127) By neglecting minimum strength utility of QFAare being developed σ in the Avrami Equation, the ability min and will be reviewed in a subsequent to successfully predict strength loses article. HTP accuracy. As discussed above, Staley showed that at lower values ofσ/σ , max the predictions are improved by intro- References ducing σ as a constant related to 1. T. Croucher, Quenching of Aluminum min Alloys: What This Key Step Accomplishes, strength in the absence of hardening Heat Treating, p 20-21, 1982. precipitates. The reader is directed to 2. J.C. Chevrier, A. Simon, G. Beck, Optimal Ref 18 for a rigorous treatment of this Cooling Rate and Process Control in approach, which permits the inclusion Metallic Parts Heat Treatment, Heat and of aging temperature variation, solu- Mass Transfer in Metallurgical Systems, Vol. 9, tion treatment temperature, and alloy p 535-544, 1981. composition to be included in the 3. P. Archambault, et, al., AContribution to model. the 7075 Heat Treatment, Materials Science (cid:127) Tiryakioglu and Shuey have devel- and Engineering, Vol. 43, p 1-6, 1980. 4. W.L. Fink and L.A. Willey, Quenching of opeda new QFAmodel that addresses 75S Aluminum Alloy, Trans. AIME, Vol. 175, many of the deficiencies of the classical p 414-427, 1948. model or even the various improve- 5. J.W. Evancho and J.T. Staley, Kinetics of ments such as establishing process- Precipitation in Aluminum Alloys During structure-property relationships, in- Continuous Cooling, Met. Trans., Vol. 5, cludes multiple quench precipitates, Jan., p. 43-47, 1974. and utilizes thermodynamic and cal- 6. J.T. Staley, Modeling Quenching of Pre- Table 3 —Effect of the time step on the quench factor calculated from a single cooling curve(a) Time step, s 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 Quench factor 1.19 1.19 1.17 1.14 1.30 1.52 1.53 1.33 (a) 38°C water flowing at 0.25 m/s. HEAT TREATING PROGRESS (cid:127) MAY/JUNE 2009 27 Quench Al.qxp 4/27/2009 2:26 PM Page 6 cipitation Strengthened Alloys: Applica- AQuench Factor Analysis of the Influence Stress Reduction in 7175-T73, 6061-T6, and tion to an Aluminum-Copper-Lithium of Water Spray Quenching on the Age- 2017A-T4 Aluminum Alloys Using Quench Alloy, Ph.D. Thesis, Drexel Univ., 1989. Hardenability of Aluminum Alloys, in Ma- Factor Analysis, J. of Matls Proc. Tech., Vol 7. C.E. Bates, Quench Optimization for Alu- terials Processing in the Computer Age, (R. 153-154, p 346-351, 2004. minum Alloys, AFS Trans., 93-25, p 1045- Voller, M.S. Stachowicz and B.G. Thomas, 22. D.D. Hall and I. Mudawar, Optimiza- 1054, 1994. Eds.), TMS, p 203-221, 1991. tion of Quench History of Aluminum Parts 8. C.E. Bates and G.E. Totten, Procedure for 16. J.T. Staley, R.D. Doherty, and A.P. Ja- for Superior Mechanical Properties, Intl J. Quenching Media Selection to Maximize worski, Improved Model to Predict Proper- Heat MassTransfer, Vol. 39, No. 1, p 81-95. Tensile Properties and Minimize Distortion ties of Aluminum Alloy Products after 1996. in Aluminum-Alloy Parts, Heat Treatment of Continuous Cooling, Met. Trans. A, Vol. 23. L.K. Ives, et. al., Processing/Microstruc- Metals, No. 4, p 89-98, 1988. 24A, p 2417-2427, 1993. ture/Property Relationships in 2024 Alu- 9. M. Avrami, Kinetics of Phase Change I, 17. G.E. Totten, G.M. Webster, and C.E. minum Alloy Plates, U.S. Dept. of Com- Jour. of Chemical Physics, Vol. 7, Feb., p 1103- Bates, Quench Factor Analysis: Step-By- merce, National Bureau of Standards 1112, 1939. Step Procedures for Experimental Deter- Technical Report NBSIR 83-2669, Jan. 1983. 10. M. Avrami, Kinetics of Phase change II, mination, Proc. 1st Intl. Non-Ferrous Pro- 24. L. Swartzendruber, et. al., Nondestruc- Jour. of Chemical Physics, Vol. 8, Feb., p 212- cessing and Technology Conf., (T. Bains tive Evaluation of Nonuniformities in 2219 224, 1940. and D.S. MacKenzie, Eds.), ASM Intl., Ma- Aluminum Alloy Plate - Relationship to 11. J.W. Cahn, The Kinetics of Grain terials Park, Ohio, p 305-312, Mar. 1997. Processing, U.S. Dept. of Commerce, Na- Boundary Nucleated Reactions, Acta Met., 18. P.A. Rometsch, M.J. Starink, and P.J. tional Bureau of Standards Technical Re- Vol. 4, p 449-459, 1956. Gregson, Improvements in Quench Factor port NBSIR 80-2069, Dec. 1980. 12. G.P. Dolan, J.S. Robinson, and A.J. Modeling, Mat. Sci. & Engrg., Vol. A339, p 25. J. Newkirk and D. MacKenzie, The Morris, Quench Factors and Residual Stress 255-/264, 2003. Jominy End Quench for Light-Weight Reduction in 7175-T73 Plate, Proc. Matls. 19. M. Tiryakioglu, R.T. Shuey, Quench Sen- Alloy Development, J. Mater. Eng. Perform., Solution Conf., Indianapolis, Ind., ASM sitivity of an Al-7% Si-0.6% Mg Alloy: Vol. 9, No. 4, p 408–41, 2000. Intl., Materials Park, Ohio, p 213-218, 2001. Characterization and Modeling, Met. and 13. C.E. Bates, Predicting Properties and Matls. Trans. B, Vol. 38B, p 575-582, Aug. For more information: George Totten, Minimizing Residual Stress in Quenched 2007. Portland State University, Department of Steel Parts, Jour. of Heat Treatment, Vol. 6, p 20. R.J. Flynn and J.S. Robinson, The Ap- Mechanical and Materials Engineering, 27-45, 1988. plication of Advances in Quench Factor Portland, Oreg.; tel: 206-788-0188; e-mail: 14. Quench Factor Analysis in Aluminum Analysis Property Prediction to the Heat [email protected]; or Lauralice C.F. Canale, Properties and Physical Metallurgy, (J.E. Treatment of 7010 Aluminium Alloy, Jour. University of São Paulo, Department of Hatch, Ed.), ASM Intl., Materials Park, of Matls. Proc. Tech., Vol. 153-154, p 674–680, Materials, Aeronautical and Automobile Ohio, p 159-164, 1984. 2004. Engineering, School of Engineering, São 15. J-S. Kim, R.C. Hoff, and D.R. Gaskell, 21. G.P. Dolan and J.S. Robinson, Residual Carlos, SP, Brazil; e-mail: [email protected]. 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